Process for producing reinforced carbon and graphite bodies

ABSTRACT

A high strength carbon or graphite body formed from a carbon or graphite fiber composite shape having fibers running in three dimensions and a carbon or graphite matrix. The fiber composite is formed by needling layers of carbon or graphite fibers to position some of the fibers of each layer into a running direction substantially perpendicular to the running direction of the layers.

United States Patent Carlson et al.

[ Nov. 13, 1973 PROCESS FOR PRODUCING REINFORCED CARBON AND GRAPHITE BODIES Inventors: Walter H. Carlson, Grand Island;

Leo C. Ehrenreich, Buffalo, both of NY.

The Carborundum Company, Niagara Falls, N.Y.

Filed: May 14, 1970 Appl. No.: 48,728

Related U.S. Application Data Division of Ser. No. 601,306, Dec. 13, 1966, Pat. No. 3,657,061.

Assignee:

U.S. Cl. 156/148, 28/722 R, 117/46 CC, 156/189,156/306,161/81,16l/98,161/154, 264/29, 264/105 Int. Cl. 1332b 31/14, B65h 81/00, D04h 5/02 Field of Search 28/722 R; 117/46 CC; 156/148,306, 189; 161/81, 88, 161/98, 154, 170, 182, 50, 80; 252/502; 264/29, 105

[56] References Cited UNITED STATES PATENTS 2,713,016 7/1955 Weiss 156/148 X 3,573,123 3/1971 Siegel et al. 156/171 3,462,340 8/1969 Hough 161/59 3,462,289 8/1969 Rohl et al. 117/46 3,312,584 4/1967 Charlton et a1 161/81 Primary Examiner-Alfred L. Leavitt Assistant ExaminerRobert A. Dawson AttorneyK. W. Brownell [57] ABSTRACT 5 Claims, No Drawings PROCESS FOR PRODUCING REINFORCED CARBON AND GRAPHITE BODIES This is a division of copending US. Pat. application Ser. No. 601,306, filed Dec. 13, 1966, now US. Pat. No. 3,657,061.

This invention relates to reinforced carbon and graphite articles and more particularly to such articles having reinforcing fibers in an interlaminar direction.

Reinforced carbon and graphite articles are being used in numerous industrial and military applications because of their excellent mechanical properties and high temperature resistance. For example reinforced carbon or graphite has been fabricated into nose cones, molds, heating elements, tubes, rods and the like. A method for making reinforced carbon and graphite articles and the properties of articles made by such method is set forth in US. Pat. application Ser. No. 478,033 entitled REINFORCED CARBON AND GRAPHITE BODIES, now US. Pat. No. 3,462,289.

As described more fully in the above-mentioned application, the reinforced carbon or graphite is produced by first forming carbon or graphite fibers into a shape, such as by stacking sheets of carbon or graphite cloth or by wrapping layers of carbon or graphite yarn or tape around a mandrel, then impregnating said shape with a suitable binder. The impregnated shape is then compressed and fired to carbonize the binder. The impregnating may be repeated as often as necessary to achieve the desired product density.

It can be seen that articles made in the above manner comprise laminations of carbon or graphite fibers bound by a carbon or graphite matrix. Such articles, although possessing excellent overall physical properties, are predisposed to failure due to delamination when subjected to high interlaminar stress. This is due to the fact that reinforcing fibers run only in the x and y direction but no fibers run between the layers of reinforcing fibers to provide reinforcing in the z direction.

Accordingly it is an object of this invention to provide carbon or graphite articles that are reinforced not only in the x and y direction but also in the z direction.

It is a further object of this invention to provide a carbon or graphite material which has a longer useful life and greater utility.

Another object of this invention is to provide a method for producing reinforced carbon or graphite having improved interlaminar strength.

Further objects and advantages of this invention will be apparent from a consideration of the following description of the embodiments described below and the novel features thereof will be particularly pointed out hereinafter in connection with the appended claims.

When used in this specification the word carbon includes all suitable forms thereof, including graphite.

The objects and advantages of this invention are achieved by forming a shape consisting of overlying layers of carbon fibers wherein a portion of the fibers of said layers have been disposed in at least an adjacent layer so as to provide interlaminar reinforcement between the layers. The fiber shape is impregnated with a suitable binder and compressed to remove excess binder. The impregnated shape is fired to carbonize the binder.

The carbon fibers used in this invention are derived from the carbonization of carbonizable material such as cellulosic fibers. Graphite fibers may be obtained by graphitizing the carbon fibers by known means. The fibers may be used as woven cloth sheets, strip, yarn or as individual fibers.

The fiber shape comprises a plurality of overlying layers of carbon or graphite fibers. The shape is formed by such means as wrapping fiber or fabric around a mandrel or by stacking sheets of reinforcing fibers until a shape of desired thickness is obtained.

Interlaminar reinforcing is achieved by disposing a portion of the fibers of each overlying layer out of their horizontal plane into at least the adjacent underlying layer. This is accomplished by a process known as needling. Needling comprises subjecting several layers of fibrous material to penetration by one or more barbed needles. The individual needles are provided with projections (barbs) located in various positions on the needle which incline outwardly toward the point of the needle. As the needle enters the fibrous material the barbs engage some of the fibers and carry them along the path of needle travel. Depending on the needle penetration and the number of layers of material to be penetrated, the barbs may engage fibers in several layers through which they pass. When the needle is withdrawn the barbs are disengaged from the fibers and the needle passes back out of the fibrous material. The fibers that had been engaged and carried by the needle barbs remain disposed in the layer to which they were carried by the needle barbs. In this manner needling arranges fibers of the layers in the interlaminar or z direction and the interlaminar fibers lock the layers of material together and provide interlaminar reinforcement.

Depending on the type of equipment used to needle the layers and the thickness of the fiber shape, all the layers can be needled together simultaneously or in a series of needling steps. That is, if the fiber shape is to be of such a thickness that the needles will not penetrate to the innermost layer of the shape, several layers of fibers can be first needled, then additional layers of fibers needled thereto until the shape is built up to its desired thickness.

It will be evident that in order to have fibers disposed in the z direction, the fibers engaged by the needles must either be sheared at some point or pulled out of the weave. In some cases it may be desirable to avoid disruption of the fibers which occurs in the normal needling process. This is accomplished by providing over the surface of a fiber shape, a layer of randomly oriented, chopped fibers. The needling operation is carried out as described, however the needle barbs become loaded with the chopped fibers and carry them into the fiber shape. The chopped fibers are deposited within the fiber shape to provide interlaminar reinforcement. The needle barbs, being loaded with chopped fibers cannot engage the fibers of the shape and thus disruption of the fiber system is avoided.

Although the needled fiber shape is normally formed from carbon fibers, it is within the scope of this invention to form a fiber shape as described above using the precursor fibers and then to carbonize the shape to form carbon fibers.

The following example illustrates more clearly the manner in which a reinforced carbon article having interlaminar reinforcement was produced according to this invention. The invention, however, is not to be construed as being limited to the particular embodiment set forth in the example.

EXAMPLE A reinforced carbon ring having a thickness of onehalf inch, an outside diameter of 8% and an inside diameter of 2% inches was produced in the following manner.

A fiber pad comprising 55 sheets of carbon cloth having a thread count of 24 X 24 2 ply 1,440 filament yarn was stacked and needled in the following manner. A stack of four sheets of carbon cloth was positioned under a needling plate containing a multiplicity of downwardly extending barbed needles. Means were provided for raising and lowering the needling plate a predetermined distance. The needling plate was moved downward causing the barbed needles to penetrate the carbon cloth stack whereupon the needle barbs engaged portions of the carbon fibers and carried them out of their horizontal plane. After penetration of the stack the needling plate was raised and the barbed needles withdrawn from the fiber stack. This process was repeated until the entire surface of the fiber stack had been subjected to the needling operation. Four more sheets were stacked on the needled fiber stack and needling was repeated as described above. The needling steps were repeated until the 55 sheets of carbon cloth had been needled together to form a pad wherein the reinforcing fibers ran not only in the x and y direction but also in the z direction.

After needling, the fiber pad was placed in an autoclave and evacuated to a pressure of at least 29 inches of mercury. The pad was then pressure impregnated with liquid furfuryl alcohol polymer catalyzed with 5 percent maleic anhydride at a pressure of 120 pounds per square inch for 1% hours. The resin impregnated pad was compressed to a thickness of about one-half inch and excess resin removed. The compressed, impregnated pad was cured under a pressure of 90 to 120 psi for 8 hours at 125 C.

After curing the pad was placed in a protective atmosphere of nitrogen and the temperature was gradually raised to 800 C to carbonize the impregnant resin. The impregnating and carbonizing steps may be repeated until the desired article density is achieved.

After carbonizing the ring was machined to final dimensions.

Articles made according to this invention represent a substantial improvement over conventional reinforced carbon and graphite articles in that not only do such articles have the excellent physical characteristics normally associated with reinforced carbon or graphite articles but they also have improved interlaminar strength due to interlaminar reinforcement. Thus the advantages of fiber reinforcement can be obtained not only in the x and y direction but also in the z direction. Articles can be produced according to this invention having a wide variety of configurations and the method disclosed herein is applicable to fiber wound and tape wound shapes as well as flat lay-up shapes.

It should be clear that the angle at which the needles penetrate the fiber layers may be varied. Thus, in some applications it may be desired to dispose the interlami nar fibers at some angle other than perpendicularly to the plane of the layer. For most applications, however, the running direction of the interlaminar will be substantially perpendicular to the layers.

While the invention has been described in connec tion with specific embodiments thereof, it will be understood that it is capable of further modification, and this specification is intended to cover any variations, uses or adaptations of the invention. It will, therefore, be recognized that the invention is not to be limited to the precise embodiments shown and described but is to be interpreted as broadly as permitted by the appended claims.

We claim: I. A process for producing a laminated reinforced ar ticle, comprising the steps of l. forming a fiber shape of a plurality of woven cloth layers of intralaminar reinforcing carbon fibers; 2. providing, over the surface of the fiber shape, a layer of randomly oriented, independent carbon fibers; 3. subjecting the layers of fibrous material to penetration by barbed needles, said needles passing first through the layer of randomly oriented, independent carbon fibers, whereby a. the needle barbs become loaded with independent carbon fibers and carry the independent carbon fibers into the fiber shape, and

b. independent carbon fibers are deposited within the fiber shape to provide interlaminar reinforcement;

4. impregnating the fiber shape with a carbonizable binder; and

S. heating the impregnated shape at a sufficiently high temperature to cure and carbonize the binder therein.

2. The process of claim 1 wherein the independent carbon fibers are chopped carbon fibers.

3. The process of claim 1 wherein said shape is needled a first time and additional layers of fibers are added and needled thereto, and repeating said adding and needling steps to build said shape to a desired num ber of layers.

4. The process of claim 1 wherein said fiber shape is formed by stacking sheets of cloth woven from said fibers.

5. The process of claim 1 wherein said shape is formed by winding layers of said fiber around a mandrel. 

2. The process of claim 1 wherein the independent carbon fibers are chopped carbon fibers.
 2. providing, over the surface of the fiber shape, a layer of randomly oriented, independent carbon fibers;
 3. The process of claim 1 wherein said shape is needled a first time and additional layers of fibers are added and needled thereto, and repeating said adding and needling steps to build said shape to a desired number of layers.
 3. subjecting the layers of fibrous material to penetration by barbed needles, said needles passing first through the layer of randomly oriented, independent carbon fibers, whereby a. the needle barbs become loaded with independent carbon fibers and carry the independent carbon fibers into the fiber shape, and b. independent carbon fibers are deposited within the fiber shape to provide interlaminar reinforcement;
 4. impregnating the fiber shape with a carbonizable binder; and
 4. The process of claim 1 wherein said fiber shape is formed by stacking sheets of cloth woven from said fibers.
 5. The process of claim 1 wherein said shape is formed by winding layers of said fiber around a mandrel.
 5. heating the impregnated shape at a sufficiently high temperature to cure and carbonize the binder therein. 